US20160298002A1 - Adhesive for metal/fabric bonding:preparation and using method - Google Patents

Adhesive for metal/fabric bonding:preparation and using method Download PDF

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Publication number
US20160298002A1
US20160298002A1 US15/034,873 US201415034873A US2016298002A1 US 20160298002 A1 US20160298002 A1 US 20160298002A1 US 201415034873 A US201415034873 A US 201415034873A US 2016298002 A1 US2016298002 A1 US 2016298002A1
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United States
Prior art keywords
adhesive
metal
fabric
stirring
epoxy resin
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US15/034,873
Inventor
Lizong Dai
Jie Mao
Fanpel Zheng
Lingnan CHEN
Zhixiong Chen
Birong Zheng
Liangjia Me
Yiting Xu
Wei'ang Luo
Xiasheng Xu
Zhaochang Wang
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Xiamen University
Fujian Longxi Bearing Group Co Ltd
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Xiamen University
Fujian Longxi Bearing Group Co Ltd
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Assigned to XIAMEN UNIVERSITY, FUJIAN LONGXI BEARING (GROUP) CORP., LTD. reassignment XIAMEN UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, Lingnan, CHEN, ZHIXIONG, DAI, Lizong, HE, Liangjia, LUO, Wei'ang, MAO, JIE, WANG, Zhaochang, XU, Xiasheng, XU, Yiting, ZENG, Birong, ZENG, FANPEL
Publication of US20160298002A1 publication Critical patent/US20160298002A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/023—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring

Definitions

  • the present invention relates to adhesive, especially to adhesive using for bonding fabric and metal.
  • Metal agglutination is a novel technology about metal-metal interfacial bonding and metal-nonmetal interfacial bonding, wherein two materials are bonded strongly via the adhesive force of adhesive disposed on solid surface.
  • bonding There are two types of bonding; one is non-structural type which mainly refers to surface coating, sealing and functional bonding, and typical non-structural adhesive includes surface coating adhesive, sealing adhesive and conductive adhesive; another one is structural type which structural units are fixed together via adhesive, the structural adhesive of which as well as bonding point should be capable of transferring stress and do not affect structural integrity or environment applicability within the scope of its design.
  • Chinese patent No. CN 1074469A discloses a adhesive of enhance modified SBR using for bonding crude rubber and aluminium with a impact strength up to 2.98 kN/m, which is better than normal phenolic resin modified duprene adhesive, however, the process is complicated.
  • Chinese patent No. CN 1273261A discloses a metal/nonmetal adhesive adding chlorosulfonated polyethylene with low preparation cost, however, the process is complicated and the adhesive is of poor heat resistance and poor ageing-resistant.
  • Chinese patent No. CN 1074469A discloses a adhesive of enhance modified SBR using for bonding crude rubber and aluminium with a impact strength up to 2.98 kN/m, which is better than normal phenolic resin modified duprene adhesive, however, the process is complicated.
  • Chinese patent No. CN 1273261A discloses a metal/nonmetal adhesive adding chlorosulfonated polyethylene with low preparation cost, however, the process is complicated and the adhesive is of poor heat resistance and poor age
  • CN 1273261A discloses an organic active gel and a method for weldbonding nonmetal and metal, wherein the interface of metal and nonmetal is welded by brazing filler metal with organic gel as transition layer to overcome welding difficulty of nonmetal.
  • the welding process is implemented under high-temperature on vacuum oven, which is energy-intensive and complicated.
  • the objective of present invention is to provide epoxy adhesive for metal/fabric bonding with high fatigue-resistant intensity and uniform stress bearing, which overcomes the bonding difficulty of traditional fabric/metal substrate and the shortcomings of ordinary epoxy resin such as hard and brittle, poor cracking resistance and low impact resistance, thereby having application value to metal/nonmetal bonding, especially to metal substrate/fabric strip of self lubricating joint bearing.
  • the present invention provides adhesive for metal/fabric bonding and method for preparing and using the same.
  • the metal mainly includes steel, aluminium and its alloys.
  • the fabric mainly includes polyamide fiber, polyester fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber and their mixture.
  • the adhesive consists of: 80 to 120 pbw of epoxy resin, 10 to 30 pbw of reactive diluent, 0.5 to 5 pbw of silane coupling agent, 0.5 to 5 pbw of metallic oxide nanopowder and 35 to 60 pbw of curing agent.
  • the epoxy resin is commercial containing two or more epoxy groups per molecule, which includes epoxy E-44, E-51, E-55, E4-2, E3-1, E4-6 and E-20.
  • the reactive diluent includes 1,6-hexanediol diacrylate, hydroxy ethyl- ⁇ -methacrylate, cresyl glycidyl ether, castor oil glycidyl ether and ethylene glycol diglycidyl ether.
  • the curing agent is amines or acid anhydrides compatible with epoxy resin, which includes ethanediamine, diethylenetriamine, m-phenylenediamine, phthalic anhydride, pyromellitic dianhydride and methylcyclohexene tetracarboxylic dianhydride.
  • the metallic oxide nanopowder includes ZnO, Al 2 O 3 , BaO and Fe 3 O 4 with particle size ranges from 20 to 200 nm.
  • the preparation method comprises the steps of:
  • the using method comprises the steps of:
  • the present invention has advantages as follows:
  • Functional groups are introduced to the surface of metal and fabric after pretreatment and enter into curing reaction of adhesive, thereby improving the adhesive strength and the peeling strength.
  • Silane coupling agent and metallic oxide nanopowder improve the bondability of metal substrate and adhesive and then improve the mechanical strength of adhesive layer. Further, the inorganic component improves the heat resistance of the material.
  • Reactive diluent reduces the brittleness of epoxy resin and improves the impact resistance of the adhesive layer as well.
  • FIG. 1 to FIG. 4 respectively illustrates peeling strength diagram of embodiment 1 to embodiment 4.
  • Aluminium substrate is cleaned by acetone, washed by deionized water and dried in oven for 1 hour to remove impurity such as oxide on the surface, then dipped into silane coupling agent and stand until the surface is dry.
  • Kevlar fabric is washed by absolute alcohol to remove impurity, dried in oven for 1 hour and impregnated in phosphoric acid for 0.5 to 1 hour, then dried.
  • the pretreatment of metal and fabric refers to embodiment 1.
  • the pretreatment of metal and fabric refers to embodiment 1.
  • the pretreatment of metal and fabric refers to embodiment 1.
  • the present invention provides epoxy adhesive for metal/fabric bonding with high fatigue-resistant intensity and uniform stress bearing, which overcomes the bonding difficulty of traditional fabric/metal substrate and the shortcomings of ordinary epoxy resin such as hard and brittle, poor cracking resistance and low impact resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A new approach for preparation and use of adhesive for metal and fabric bonding is proposed in this invention. Generally, 80-120 g of epoxy resin, 10-30 g of reactive diluent, 0.5-5 g siliane coupling agent, 0.5-5 g metallic oxide nanopowder and 35-60 g curing agent are applied in the formula. With the treatment of silane coupling agent and the mixture of phosphoric acid and nitric acid respectively, the active groups are introduced onto the surface of the metal and the fabric, which enhanced the adhesive strength of metal/fabric interface. Simultaneously, the brittleness, poor cracking and impact resistance of the traditional epoxy adhesive are also optimized by using the method of this invention, which is easy to operate and widely used.

Description

    FIELD OF THE INVENTION
  • The present invention relates to adhesive, especially to adhesive using for bonding fabric and metal.
    • BACKGROUND OF THE INVENTION
  • Metal agglutination is a novel technology about metal-metal interfacial bonding and metal-nonmetal interfacial bonding, wherein two materials are bonded strongly via the adhesive force of adhesive disposed on solid surface. There are two types of bonding; one is non-structural type which mainly refers to surface coating, sealing and functional bonding, and typical non-structural adhesive includes surface coating adhesive, sealing adhesive and conductive adhesive; another one is structural type which structural units are fixed together via adhesive, the structural adhesive of which as well as bonding point should be capable of transferring stress and do not affect structural integrity or environment applicability within the scope of its design.
  • Recent years, function materials composed by metal and nonmetal take a more and more important role in the fields of space flight and war industry. However, adhesive is difficult to form stable binding layer with metal and nonmetal due to their different properties, which affects the bonding intensity of composite material. The application of metal agglutination is limited by low peel strength, poor impact strength and short fatigue-resistant time, and therefore it is important to find a simple and practicable method for metal and nonmetal bonding.
  • Chinese patent No. CN 1074469A discloses a adhesive of enhance modified SBR using for bonding crude rubber and aluminium with a impact strength up to 2.98 kN/m, which is better than normal phenolic resin modified duprene adhesive, however, the process is complicated. Chinese patent No. CN 1273261A discloses a metal/nonmetal adhesive adding chlorosulfonated polyethylene with low preparation cost, however, the process is complicated and the adhesive is of poor heat resistance and poor ageing-resistant. Chinese patent No. CN 1273261A discloses an organic active gel and a method for weldbonding nonmetal and metal, wherein the interface of metal and nonmetal is welded by brazing filler metal with organic gel as transition layer to overcome welding difficulty of nonmetal. However, the welding process is implemented under high-temperature on vacuum oven, which is energy-intensive and complicated.
    • SUMMARY OF THE INVENTION
  • The objective of present invention is to provide epoxy adhesive for metal/fabric bonding with high fatigue-resistant intensity and uniform stress bearing, which overcomes the bonding difficulty of traditional fabric/metal substrate and the shortcomings of ordinary epoxy resin such as hard and brittle, poor cracking resistance and low impact resistance, thereby having application value to metal/nonmetal bonding, especially to metal substrate/fabric strip of self lubricating joint bearing.
  • The present invention provides adhesive for metal/fabric bonding and method for preparing and using the same.
  • The metal mainly includes steel, aluminium and its alloys.
  • The fabric mainly includes polyamide fiber, polyester fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber and their mixture.
  • The adhesive consists of: 80 to 120 pbw of epoxy resin, 10 to 30 pbw of reactive diluent, 0.5 to 5 pbw of silane coupling agent, 0.5 to 5 pbw of metallic oxide nanopowder and 35 to 60 pbw of curing agent.
  • The epoxy resin is commercial containing two or more epoxy groups per molecule, which includes epoxy E-44, E-51, E-55, E4-2, E3-1, E4-6 and E-20.
  • The reactive diluent includes 1,6-hexanediol diacrylate, hydroxy ethyl-β-methacrylate, cresyl glycidyl ether, castor oil glycidyl ether and ethylene glycol diglycidyl ether.
  • The formula of the silane coupling agent is Y(CH2)nSiX3, wherein n=0˜3; X refers to chlor group, methoxy group, methoxy group, methoxyethoxy group or acetoxyl group, and Y refers to amino-group or epoxy group.
  • The curing agent is amines or acid anhydrides compatible with epoxy resin, which includes ethanediamine, diethylenetriamine, m-phenylenediamine, phthalic anhydride, pyromellitic dianhydride and methylcyclohexene tetracarboxylic dianhydride.
  • The metallic oxide nanopowder includes ZnO, Al2O3, BaO and Fe3O4 with particle size ranges from 20 to 200 nm.
  • The preparation method comprises the steps of:
  • dissolving metallic oxide nanopowder, silane coupling agent, curing agent onto reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
  • adding epoxy resin into the emulsion in portions during ultrasonic and stirring for 0.5 to 2 hours until homogeneous mixed.
  • The using method comprises the steps of:
  • preparing a metal substrate via cleaning by acetone, washing by deionized water, drying, coating the silane coupling agent and standing for 0.5-1 hour;
  • impregnating the fabric in a mixture solution of phosphoric acid and nitric acid with a volume ratio ranges from 1:9 to 4:6 at 40° C.-60° C. for 0.5-2 hours, wherein the concentration of phosphoric acid ranges from 1 to 3 mol/L, and the concentration of nitric acid ranges from 1 to 3 mol/L;
  • coating the adhesive on the surface of the metal substrate and covering the fabric on the adhesive for drying and press curing.
  • Comparing to the existing technology, the present invention has advantages as follows:
  • 1. Functional groups are introduced to the surface of metal and fabric after pretreatment and enter into curing reaction of adhesive, thereby improving the adhesive strength and the peeling strength.
  • 2. Silane coupling agent and metallic oxide nanopowder improve the bondability of metal substrate and adhesive and then improve the mechanical strength of adhesive layer. Further, the inorganic component improves the heat resistance of the material.
  • 3. Reactive diluent reduces the brittleness of epoxy resin and improves the impact resistance of the adhesive layer as well.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 to FIG. 4 respectively illustrates peeling strength diagram of embodiment 1 to embodiment 4.
    •  DETAILED DESCRIPTION OF THE EMBODIMENTS
  • The present invention will be further described with the drawings and the embodiments.
    • Embodiment 1
  • Aluminium substrate is cleaned by acetone, washed by deionized water and dried in oven for 1 hour to remove impurity such as oxide on the surface, then dipped into silane coupling agent and stand until the surface is dry. Kevlar fabric is washed by absolute alcohol to remove impurity, dried in oven for 1 hour and impregnated in phosphoric acid for 0.5 to 1 hour, then dried.
  • 1 g Al2O3 nanopowder, 10 ml ethylene glycol diglycidyl ether, 0.5 g γ-glycidoxy propyl trimethoxy silane, 40 g 4,4-diaminodiphenyl sulfone are dissolved into 35 ml acetone in turn and stirred for 1 hour, then 90 g epoxy resin E51 is added into the emulsion in ten portions during ultrasonic and stirred for 1 hour to obtain adhesive. The adhesive is coated on the surface of prepared aluminium substrate, and the prepared Kevlar fabric is covered on the adhesive. Then the composite is dried in oven at 50° C. for 1 hour, heated to 160° C. in 2 hours to cure for 2 hours under 0.2 MPa pressure. After curing, the peeling strength of the composite is 0.82 N/mm measured by cupping machine.
    • Embodiment 2
  • The pretreatment of metal and fabric refers to embodiment 1.
  • 1 g Al2O3 nanopowder, 15 ml ethylene glycol diglycidyl ether, 1 g γ-glycidoxy propyl trimethoxy silane, 50 g 4,4-diaminodiphenyl sulfone are dissolved into 35 ml acetone in turn and stirred for 1 hour, then 100 g epoxy resin E51 is added into the emulsion in ten portions during ultrasonic and stirred for 1 hour to obtain adhesive. The adhesive is coated on the surface of prepared aluminium substrate, and the prepared Kevlar fabric is covered on the adhesive. Then the composite is dried in oven at 50° C. for 1 hour, heated to 160° C. in 2 hours to cure for 2 hours under 0.2 MPa pressure. After curing, the peeling strength of the composite is 1.17 N/mm measured by cupping machine.
    • Embodiment 3
  • The pretreatment of metal and fabric refers to embodiment 1.
  • 0.5 g Al2O3 nanopowder, 10 ml ethylene glycol diglycidyl ether, 1 g γ-glycidoxy propyl trimethoxy silane, 60 g 4,4-diaminodiphenyl sulfone are dissolved into 35 ml acetone in turn and stirred for 1 hour, then 120 g epoxy resin E51 is added into the emulsion in ten portions during ultrasonic and stirred for 1 hour to obtain adhesive. The adhesive is coated on the surface of prepared aluminium substrate, and the prepared Kevlar fabric is covered on the adhesive. Then the composite is dried in oven at 50° C. for 1 hour, heated to 160° C. in 2 hours to cure for 2 hours under 0.2 MPa pressure. After curing, the peeling strength of the composite is 1.03 N/mm measured by cupping machine.
    • Embodiment 4
  • The pretreatment of metal and fabric refers to embodiment 1.
  • 1 g Al2O3 nanopowder, 20 ml ethylene glycol diglycidyl ether, 0.5 g γ-glycidoxy propyl trimethoxy silane, 55 g 4,4-diaminodiphenyl sulfone are dissolved into 35 ml acetone in turn and stirred for 1 hour, then 100 g epoxy resin E51 is added into the emulsion in ten portions during ultrasonic and stirred for 1 hour to obtain adhesive. The adhesive is coated on the surface of prepared aluminium substrate, and the prepared Kevlar fabric is covered on the adhesive. Then the composite is dried in oven at 50° C. for 1 hour, heated to 160° C. in 2 hours to cure for 2 hours under 0.2 MPa pressure. After curing, the peeling strength of the composite is 1.42 N/mm measured by cupping machine.
    • INDUSTRIAL APPLICABILITY
  • The present invention provides epoxy adhesive for metal/fabric bonding with high fatigue-resistant intensity and uniform stress bearing, which overcomes the bonding difficulty of traditional fabric/metal substrate and the shortcomings of ordinary epoxy resin such as hard and brittle, poor cracking resistance and low impact resistance.

Claims (12)

1. An adhesive for metal/fabric bonding of which the metals mainly include steel aluminium and their alloys, while the fabric mainly includes polyamide fiber, polyester fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber, polyvinyl alcohol fiber and their mixture; the adhesive consists of:
80 g to 120 g of epoxy resin, 10 g to 30 g of a reactive diluent, 0.5 g to 5 g of a silane coupling agent, 0.5 g to 5 g of a metallic oxide nanopowder and 35 g to 60 g of a curing agent;
the method of using the adhesive comprises the steps of:
preparing a metal substrate via cleaning by acetone, washing by deionized water, drying, coating the silane coupling agent and standing for 0.5-1 hour;
impregnating the fabric into a mixture solution of phosphoric acid and nitric acid with a volume ratio ranges from 1:9 to 4:6 at 40° C.-60° C. for 0.5-2 hours, wherein the concentration of phosphoric acid ranges from 1 to 3 mol/L, and the concentration of nitric acid ranges from 1 to 3 mol/L;
coating the adhesive on the surface of the metal substrate and covering the fabric on the adhesive for further drying and press curing.
2. The adhesive for metal/fabric needing according to claim 1, wherein the epoxy resin is commercial containing two or more epoxy groups per molecule, which includes epoxy E-44, E-51, E-55, E4-2, E3-1, E4-6 and E-20.
3. The adhesive for metal/fabric bonding according to claim 2, wherein the reactive diluent includes 1,6-hexanediol diacrylate, hydroxyethyl-β-methacrylate, cresyl glycidyl ether, castor oil glycidyl ether and ethylene glycol diglycidyl ether.
4. The adhesive for metal/fabric bonding according to claim 3, wherein the formula of the silane coupling agent is Y(CH2)nSiX3, wherein n=0˜3; X refers to chloro group, methoxy group, methoxy group, methoxyethoxy group or acetoxyl group, and Y refers to amino-group or epoxy group.
5. The adhesive for metal/fabric bonding according to claim 4, wherein the curing agent is amines or acid anhydrides compatible with epoxy resin, which includes ethanediamine, diethylenetriamine, m-phenylenediamine, phthalic anhydride, pyromellitic dianhydride and methylcyclohexene tetracarboxylic dianhydride.
6. The adhesive for metal/fabric bonding according to claim 5, wherein the metallic oxide nanopowder includes ZnO, Al2O3, BaO and Fe3O4 with particle size ranging from 20 to 200 nm.
7. The adhesive for metal/fabric bonding according to claim 1, wherein the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent, the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in batches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
8. The adhesive for metal/fabric bonding according to claim 2, wherein the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent, the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in batches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
9. The adhesive for metal/fabric bonding according to claim 3, wherein the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent, the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in batches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
10. The adhesive for metal/fabric bonding according to claim 4, wherein the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent, the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in batches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
11. The adhesive for metal/fabric bonding according to claim 5, wherein the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in batches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
12. The adhesive for metal/fabric bonding according in claim 6, wherein; the preparation method comprises the steps of:
firstly, dissolving the metallic oxide nanopowder, the silane coupling agent the curing agent onto the reactive diluent in turn and stirring for 0.5 to 1 hour to obtain homogeneous emulsion;
secondly, adding epoxy resin into the emulsion in hatches during ultrasonic and stirring for 0.5 to 2 hours until they are homogeneously mixed.
US15/034,873 2013-11-06 2014-11-05 Adhesive for metal/fabric bonding:preparation and using method Abandoned US20160298002A1 (en)

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